CN102993535B - Polyethylene resin composition used for tube materials - Google Patents
Polyethylene resin composition used for tube materials Download PDFInfo
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- CN102993535B CN102993535B CN201110265138.0A CN201110265138A CN102993535B CN 102993535 B CN102993535 B CN 102993535B CN 201110265138 A CN201110265138 A CN 201110265138A CN 102993535 B CN102993535 B CN 102993535B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention aims at providing a polyethylene tube material resin composition. According to the invention, HDPE resin is adopted as a base material; and mLLDPE weather-resistant masterbatch and organic peroxide micro-crosslinking modification is carried out, such that the obtained tube material resin composition is provided with excellent ESCR performance (greater than 2500h). The invention further provides a preparation method of the composition. Calculated according to the weight of high density polyethylene (HDPE) as 100%, the resin composition comprises: 100% of HDPE, 0.05-0.2% of a complex crosslinking auxiliary agent, and 10-30% of mLLDPE weather-resistant masterbatch. The mLLDPE weather-resistant masterbatch is a blend composed of polymer mLLDPE, a composite light stabilizer, an mLLDPE-g-MAH graft (a graft of mLLDPE and maleic anhydride), and a dispersing agent. A tube material prepared by using the composition has excellent performances, and can be widely applied in fields such as water supply, agricultural irrigation, fuel gas transportation, sewage discharging, chemicals, and postal telecommunications.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition, the tubing resin combination with good environmental stress cracking resistance that to be specifically related to take high density polyethylene(HDPE) (HDPE) be base-material.
Background technology
In recent years, development along with plastics industry, polyvinyl piping materials so that it is lightweight, corrosion-resistant, thermal conductivity is low, good insulation preformance, construction and installation and the feature such as easy to maintenance be more and more subject to people's attention, and become after PVC, the plastic conduit kind of world consumption amount maximum, Application Areas spreads all over the fields such as the engineerings such as feedwater, agricultural irrigation, combustion gas conveying, blowdown, mine mortar conveying and oil field, chemical industry and post and telecommunications.
In polyvinyl piping materials, high density polyethylene(HDPE) (HDPE) pipe has the features such as light weight, mechanical property excellence, crimp tendency and flexibility are good, is the tubing kind that has competitive capacity most.But structure, form due to HDPE resin itself, easily cause tubing to there will be fracture phenomena under certain hour, certain load effect, be that environmental stress cracking resistance (ESCR) is poor, thereby affected HDPE tubing, in outdoor water supply pipe, gas line, irrigation, use the application in the fields such as pipe.Therefore, ESCR is an important indicator evaluating and affect the HDPE tubing life-span.
< < supplies water and with polyvinyl piping materials standard > > (ISO 4427:1996), according to tubing longterm strength, PE is divided into the different gradess such as PE 32, PE40, PE 63, PE 80, PE 100.In China, on market, modal tubing speciality resin is PE63 level, as trades mark such as 6100M, HD4810EX.The ESCR of PE63 grade resins is all less than 1000 hours, has therefore limited use range, and price and class all cannot contend with PE80, other tubing speciality resin of PE100 level.And the polyvinyl piping materials of PE80, PE100 or higher category is resin dedicated, ESCR is all over 1000 hours, but resin is directly to obtain from polyreaction, and technical sophistication and cost are higher.
There are some researches show, the ESCR of HDPE resin is not only subject to the impact of the extraneous factors such as temperature, external force, and larger with the relation of the internal factor such as the molecular weight of resin itself, molecular weight distribution, the degree of branching and a chain length, crystallization situation.Therefore, in prior art, there is the angle from polymerization, by reactors in series, add long-chain branch monomer, control reaction conditions, change the polyvinyl resin that the modes such as catalyst system can be produced high ESCR, as reports such as CN1903896, CN1513002.But be more the angle from the modification of resin post-treatment, by modulation resinous molecular structure, improve the ESCR of material, main path has two kinds: the one, and in resin, sneak into the second components such as polyolefine, elastomerics and carry out modification, the effect that second component plays refinement spherocrystal, reduces degree of crystallinity and stop crackle to stretch in polyethylene.The method is current the most frequently used method, relevant report is more, as CN1556835, CN1247204, CN1262972, US2007282071 (A1), US2006276593 (A1), US2003088021 (A1), US7153909, WO0105852 (A1), JP57031945 (A) etc.The 2nd, by chemical crosslinking modified, form crosslinked structure, increase the connection between molecular chain, improve the environmental stress cracking resistance of polythene material.As CN2492729 adopts organosilane crosslinked polyethylene layer; ZL 0215154804 adopts a kind of novel silane crosslinked polyethylene to produce for tubing.ZL03825881.1 utilizes peroxide crosslinked polyethylene to manufacture cross-linked polyethylene pipe.US4390666 mixes the polyvinyl resin of two kinds of different molecular weights, and the polyethylene composition that recycling organo-peroxide is cross-linked preparation has good physical property, as has high rigidity, high ESCR, high impact resistance etc.; CN200410066408.5, by with infrared irridiation, promotes peroxide crosslinked polyethylene resin in preparing the process of tubing, thus the mechanical property of raising polyvinyl piping materials and resistance toheat etc.
Summary of the invention
The object of the invention is to provide a kind of polyethylene resin composition for pipe, take HDPE resin as base-material, by the weather-proof master batch of metallocene linear-low density polyethylene (mLLDPE) and micro-cross-linking modified realization of organo-peroxide.This resin combination has good ESCR performance (> 2500 hours).The present invention further proposes the preparation method of composition.
The weight of high density polyethylene(HDPE) (HDPE) of take is that absolutely resin combination of the present invention comprises:
1)HDPE 100％；
2) composite crosslinking coagent 0.05%～0.2%;
3) the weather-proof master batch 10%～30% of mLLDPE;
Wherein said composite crosslinking coagent is tertbutyl peroxide (TBHP) and dibenzoyl peroxide (BPO), and the mass ratio of two kinds of linking agents is TBHP/BPO=25: 1～5: 1.
The blend that the weather-proof master batch of described mLLDPE is comprised of grafts (mLLDPE-g-MAH) and the dispersion agent of mLLDPE, composite light stabilizer, mLLDPE and maleic anhydride (MAH).Polymkeric substance mLLDPE to be to adopt single site catalysts---polyethylene prepared by metallocene catalysis system, can be ethene and butene-1, hexene-1 copolymerization and obtain, and also can be obtained by ethylene homo.Density: 0.865～0.941g/cm3 wherein, melt flow rate (MFR): 0.5～10g/10min.Described melt flow rate (MFR) (MFR) is at 190 ℃, the measured value under 2.16Kg load.
The compound system that composite light stabilizer is comprised of quencher and radical scavenger.Quencher is organic nickel compound, as: two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab 2002), 2,2-thiobis (the tertiary octyl phenol oxygen of 4-base) nickel-n-Butyl Amine 99 complex compound (UV-1084), 2,2-thiobis (the tertiary octyl phenol oxygen of 4-base) nickel (AM-101), dioctyl dithiocarbamic acid nickel (AM-108), N, a kind of in N-nickel dibutyl dithiocarbamate (NBC), organic nickel compound is because of the toxicity problem of heavy metal ion, and its consumption should be strict controlled in 0.01%～0.04% (by the weight percent meter of mLLDPE).Radical scavenger is selected the hindered amine as light stabilizer (HALS) with space steric effect, as: a kind of in Tinuvin123, Tinuvin622, Tinuvin791, Tinuvin328, Tinuvin326, GW-540, GW-480, GW-544, CH944, its consumption is 0.1%～0.5% (by the weight percent meter of mLLDPE).This compound system can reduce the excited state functional group in the molecular resin after cross-linking modified with reactive behavior effectively, promptly catch free radical R, ROO that linking agent produces, destroy the growth of living chain, improve the stability of base resin molecular structure, reached the work-ing life that extends resin.
MLLDPE-g-MAH is grafted to grafted monomer the graft copolymer on mLLDPE main chain under the effect of initiator; initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate (TBPA), tertbutyl peroxide, 2; 5-dimethyl-2; a kind of in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or peroxide di-t-butyl, preferably adopts dicumyl peroxide (DCP).Grafted monomer maleic anhydride (MAH) is commercial goods.
Dispersion agent can be wherein a kind of or composite such as sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, white oil, preferably adopts white oil.
The weather-proof agglomerate preparation method of mLLDPE provided by the invention comprises:
(1) preparation method of mLLDPE-g-MAH grafts:
Press the weight percent meter of mLLDPE, by the MAH of 5～10 parts (in advance chip solid being ground to form >=100 object powdered granules) and acetone, be within 1: 3～1: 5, to be mixed with mixing solutions by weight, by the mLLDPE high-speed mixing 3～5min of mixing solutions and 100 parts, the material mixing is placed to 1～2hr in encloses container again; Then initiator and the acetone of getting 0.01～0.1 part are within 1: 10～1: 20, to be mixed with mixing solutions by weight, again by mixing solutions and the mixture high-speed mixing 3～5min placing, finally by carrying out melting graft reaction in twin screw extruder, 160～220 ℃ of temperature of reaction, reaction times 3～5min, extrude, cooling, granulation, obtain MAH percentage of grafting and be 1～3% mLLDPE-g-MAH grafts.
(2) preparation of the weather-proof master batch of mLLDPE:
Press the weight percent meter of mLLDPE, together with the mLLDPE of 100 parts and the mLLDPE-g-MAH grafts of 3～8 parts, the dispersion agent of 0.5～1.0 part, put in super mixer high-speed mixing 3～5min; And then add the composite light stabilizer of 0.11～0.54 part, high-speed mixing 5～10min; Mixed material is added to twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, obtains the weather-proof master batch of mLLDPE.
The high density polyethylene(HDPE) of HDPE described in composition for adopting efficient ziegler-natta catalyst systems to prepare, MFR:0.1～10g/10min; Density: 0.945～0.957g/cm
3; Mw:10～20 * 10
4; Mw/Mn:10～20, molecular weight can be unimodal distribution, can be also bimodal distribution.Middle-high density polyethylene of the present invention can be powdery or granular resin, but best with powdered resin for reaching better mixed effect.
Composite crosslinking coagent described in composition is that TBHP and BPO are by the composite composition of different ratios.Wherein the scope of total add-on of composite crosslinking coagent is that the optimum mixture ratio of 0.05%～0.2%, two kinds of crosslinking coagents is TBHP/BPO=20: 1～10: 1.Two kinds of superoxide are commercially available prod, and its half life temperature is because of manufacturer's difference difference slightly, transformation period T=246～267 of general TBHP ℃/1min; Transformation period T=131～134 of BPO ℃/1min.
The preparation of resin combination of the present invention also can be carried out in Banbury mixer, kneader, forcing machine, but take twin screw extruder as best.
Particularly, the preparation method of polyethylene pipe resins composition provided by the invention comprises: after first two kinds of crosslinking coagents are composite in proportion, add solvent, add again the HDPE that accounts for total amount 5%～10% (wt), then, after high-speed mixing 3～5min, make premix masterbatch; Then remaining HDPE, premix masterbatch and the weather-proof master batch of mLLDPE are joined together and in forcing machine, carried out extrusion reaction by charging opening, temperature of reaction is 160～220 ℃, reaction times is 3～5min, extrudes, cooling, granulation, makes polyethylene pipe resins composition.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of the weather-proof master batch of mLLDPE and polyethylene pipe resins composition, and its total add-on is 0.2%～0.5% (take HDPE weight be per-cent).Wherein, oxidation inhibitor can be one or several compounds in phenols, hindered amines, phosphite ester kind antioxidant, and its consumption is 0.1%～0.2%.Thermo-stabilizer can be stearates, and as Zinic stearas, calcium stearate etc., consumption is generally 0.1%～0.3%.
In resin combination preparation process of the present invention, in composite crosslinking coagent, add solvent, described solvent is a kind of in toluene, dimethylbenzene, acetone, and its add-on is 2～4 times of composite crosslinking coagent weight.
In composition of the present invention, on the one hand, in the weather-proof master batch of mLLDPE, mLLDPE-g-MAH grafts has improved the consistency of resin and photostabilizer, has improved the dispersion effect of photostabilizer in resin; MLLDPE-g-MAH grafts has certain adsorption to photostabilizer in addition, has avoided the migration of photostabilizer in resin and has separated out problem, has greatly improved persistence and the high efficiency of photostabilizer.Secondly, mLLDPE molecular weight distribution (MWD) is narrow, many, the compound with regular structure of short-chain branch in molecular structure, have more complete crystal formation, can reduce refraction and the range of light in resin, can improve the ESCR performance of base resin HDPE.So mLLDPE and photostabilizer will produce certain positive cooperativity simultaneously.Select the mode with the weather-proof master batch blending of mLLDPE with HDPE, not only the ESCR performance of raising polyethylene pipe resins is had to fairly obvious effect, and reached photostabilizer and obtain best ESCR performance with minimum add-on, minimum cost.
On the other hand, select two kinds of transformation period to differ the composite cross-linking system that larger superoxide forms, can effectively control cross-linked speed and the crosslinking degree of base resin, realize micro-crosslinking structure, guaranteeing under the prerequisite of processibility, give the physical property that resin is good, especially environmental stress cracking resistance.Like this, make said composition can in the common pipe extruder group without any transformation, stably process the tubing of various internal diameters, and there is good environmental stress cracking resistance (> 2500h) with the tubing that this resin combination processes.Solved the problem of common HDPE resin environmental stress crack resistance deficiency.
Embodiment
(1) raw material
1) resin
2) superoxide
3) auxiliary agent
(2) performance test standard
(3) equipment and instrument
Φ 67 twin-screw extrusion captain/footpath=34/1 German Lestreiz companies
10 liters of high-speed mixer Fuxin plastics machinery factories
Embodiment and comparative example
Enumerate following examples invention effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment, in composition, each component is in the parts by weight of base resin HDPE.
Embodiment 1
(1) preparation of mLLDPE-g-MAH grafts: the weight percent meter of pressing mLLDPE, the MAH of 6 parts (in advance chip solid being ground to form >=100 object powdered granules) is mixed into solution with the acetone of 20 parts, by the mLLDPE high-speed mixing 3min of mixing solutions and 100 parts, the material mixing is placed to 2h in encloses container again; Then the acetone of getting 0.03 part of DCP and 0.3 part is put into beaker and is mixed, then the solution mixing is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing, 0.15 part of antioxidant 1010,0.15 part of calcium stearate; Finally the material mixing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,190,200,220,190,180,175,170; Carry out melting graft reaction, after reaction 3min, extrude, cooling, granulation, obtain mLLDPE-g-MAH grafts (percentage of grafting: 1.7%).
(2) preparation of the weather-proof master batch of mLLDPE: the weight percent meter of pressing mLLDPE, 1.7%), the white oil 5# of 0.6 part puts in high-speed mixer together, high-speed mixing 5min by the mLLDPE-g-MAH grafts of the mLLDPE of 100 parts (350) and 4 parts (percentage of grafting:; And then add the hindered amine as light stabilizer CH944 of 0.22 part and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.02 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch a of mLLDPE.
(3) preparation of polyethylene pipe resins composition: after 0.002 part of BPO and 0.048 part of TBHP are mixed with 0.2 part of acetone solvent, then add 5 parts of HDPE (6100M) pellet resin, mix 5min in 10 liters of high-speed mixers, make premix masterbatch; Take out 13 parts of weather-proof master batch a of mLLDPE and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 2
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: after 0.003 part of BPO and 0.06 part of TBHP are mixed with 0.2 part of acetone solvent, then add 5 parts of HDPE (6100M) pellet resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 15 parts of weather-proof master batch a of mLLDPE and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 3
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: after 0.004 part of BPO and 0.07 part of TBHP are mixed with 0.2 part of acetone solvent, then add 5 parts of HDPE (6100M) pellet resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 17 parts of weather-proof master batch a of mLLDPE and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 4
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: after 0.005 part of BPO and 0.09 part of TBHP are mixed with 0.3 part of acetone solvent, then add 5 parts of HDPE (6100M) pellet resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 20 parts of weather-proof master batch a of mLLDPE and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 5
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: after 0.012 part of BPO and 0.13 part of TBHP are mixed with 0.4 part of acetone solvent, then add 5 parts of HDPE (6100M) pellet resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 21 parts of weather-proof master batch a of mLLDPE and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 6
(1) preparation of mLLDPE-g-MAH grafts: the weight percent meter of pressing mLLDPE, the MAH of 7 parts (in advance chip solid being ground to form >=100 object powdered granules) is mixed into solution with the acetone of 30 parts, by the mLLDPE high-speed mixing 3min of mixing solutions and 100 parts, the material mixing is placed to 2h in encloses container again; Then the acetone of getting 0.05 part of DCP and 0.5 part is put into beaker and is mixed, then the solution mixing is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing, 0.2 part of antioxidant 1010,0.1 part of calcium stearate; Finally the material mixing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,190,200,220,190,180,175,170; Carry out melting graft reaction, after reaction 3min, extrude, cooling, granulation, obtain mLLDPE-g-MAH grafts (percentage of grafting: 1.9%).
(2) preparation of the weather-proof master batch of mLLDPE: the weight percent meter of pressing mLLDPE, 1.9%), the white oil 5# of 0.7 part puts in high-speed mixer together, high-speed mixing 5min by the mLLDPE-g-MAH grafts of the mLLDPE of 100 parts (350) and 5 parts (percentage of grafting:; And then add the hindered amine as light stabilizer CH944 of 0.31 part and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.025 part, 0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch b of mLLDPE.
(3) preparation of polyethylene pipe resins composition: after 0.006 part of BPO and 0.1 part of TBHP are mixed with 0.3 part of acetone solvent, then add 5 parts of HDPE (60550) powder resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 22 parts of weather-proof master batch b of mLLDPE and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 7
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 6.
(3) preparation of polyethylene pipe resins composition: after 0.007 part of BPO and 0.12 part of TBHP are mixed with 0.5 part of acetone solvent, then add 5 parts of HDPE (60550) powder resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 25 parts of weather-proof master batch b of mLLDPE and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 8
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 6.
(3) preparation of polyethylene pipe resins composition: after 0.008 part of BPO and 0.11 part of TBHP are mixed with 0.5 part of acetone solvent, then add 5 parts of HDPE (60550) powder resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 27 parts of weather-proof master batch b of mLLDPE and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 9
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 6.
(3) preparation of polyethylene pipe resins composition: after 0.014 part of BPO and 0.17 part of TBHP are mixed with 0.5 part of acetone solvent, then add 5 parts of HDPE (60550) powder resin, mix 3min in 10 liters of high-speed mixers, make premix masterbatch; Take out 28 parts of weather-proof master batch b of mLLDPE and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Embodiment 10
(1) preparation of mLLDPE-g-MAH grafts: the weight percent meter of pressing mLLDPE, the MAH of 8 parts (in advance chip solid being ground to form >=100 object powdered granules) is mixed into solution with the acetone of 30 parts, by the mLLDPE high-speed mixing 3min of mixing solutions and 100 parts, the material mixing is placed to 2h in encloses container again; Then the acetone of getting 0.07 part of DTBP and 0.8 part is put into beaker and is mixed, then the solution mixing is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing, 0.15 part of antioxidant 1010,0.2 part of calcium stearate; Finally the material mixing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,190,200,220,190,180,175,170; Carry out melting graft reaction, after reaction 3min, extrude, cooling, granulation, obtain mLLDPE-g-MAH grafts (percentage of grafting: 2.3%).
(2) preparation of the weather-proof master batch of mLLDPE: the weight percent meter of pressing mLLDPE, 2.3%), the white oil 5# of 0.8 part puts in high-speed mixer together, high-speed mixing 5min by the mLLDPE-g-MAH grafts of the mLLDPE of 100 parts (350) and 7 parts (percentage of grafting:; And then add the hindered amine as light stabilizer Tinuvin 791 of 0.42 part and the quencher NBC of 0.03 part, 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch c of mLLDPE.
(3) preparation of polyethylene pipe resins composition: after 0.015 part of BPO and 0.15 part of TBHP are mixed with 0.5 part of xylene solvent, then add 5 parts of HDPE (60550) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 29 parts of weather-proof master batch c of mLLDPE and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 1
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: difference is not add BPO in composition preparation process, and the add-on of TBHP is 0.05 part, and other condition is identical with embodiment 1, prepares polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 2
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: difference is not add TBHP in composition preparation process, and the add-on of BPO is 0.063 part, and other condition is identical with embodiment 2, prepares polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 3
(1) preparation of the weather-proof master batch of mLLDPE: difference is not add mLLDPE-g-MAH grafts in the weather-proof master batch preparation process of mLLDPE, and other processes are identical with embodiment 1, make the weather-proof master batch of mLLDPE (a-1).
(2) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 3, difference is that the weather-proof master batch of the mLLDPE adding in composition preparation process is not containing mLLDPE-g-MAH grafts, 17 parts of the add-ons of the weather-proof master batch of mLLDPE (a-1), that is: 0.004 part of BPO and 0.07 part of TBHP are mixed with 0.2 part of acetone solvent after, then add 5 parts of HDPE (6100M) pellet resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 17 parts of weather-proof master batches of mLLDPE (a-1) and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 4
The preparation of polyethylene pipe resins composition: difference is not add the weather-proof master batch a of mLLDPE in resin combination preparation process, and other processes are identical with embodiment 4, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 5
The preparation of polyethylene pipe resins composition: other condition is identical with embodiment 5, difference is not add in composition preparation process the weather-proof master batch a of mLLDPE, but add mLLDPE (ECD350), 21 parts of the add-ons of mLLDPE (ECD350), that is: 0.012 part of BPO and 0.13 part of TBHP are mixed with 0.4 part of acetone solvent after, then add 5 parts of HDPE (6100M) pellet resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 21 parts of mLLDPE (ECD350) and premix masterbatch and 95 parts of HDPE (6100M) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 6
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of mLLDPE: difference is not add quencher 2002 in the weather-proof master batch preparation process of mLLDPE, the add-on of hindered amine as light stabilizer CH944 is 0.335 part, other processes are identical with embodiment 5, make the weather-proof master batch of mLLDPE (b-1).
(3) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 6, difference is that the weather-proof master batch of the mLLDPE adding in composition preparation process is not containing quencher 2002,22 parts of the add-ons of the weather-proof master batch of mLLDPE (b-1), that is: 0.006 part of BPO and 0.1 part of TBHP are mixed with 0.3 part of acetone solvent after, then add 5 parts of HDPE (60550) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 22 parts of weather-proof master batches of mLLDPE (b-1) and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 7
(1) preparation of mLLDPE-g-MAH grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of mLLDPE is completely identical with embodiment 6.
(3) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 7, difference is that the add-on of the weather-proof master batch b of mLLDPE in composition preparation process is 5 parts, that is: 0.007 part of BPO and 0.12 part of TBHP are mixed with 0.5 part of acetone solvent after, then add 5 parts of HDPE (60550) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 5 parts of weather-proof master batch b of mLLDPE and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 8
The preparation of polyethylene pipe resins composition: other condition is identical with embodiment 8, difference is not add in composition preparation process the weather-proof master batch b of mLLDPE, but add mLLDPE (ECD 350), 27 parts of the add-ons of mLLDPE (ECD 350), that is: 0.008 part of BPO and 0.11 part of TBHP are mixed with 0.5 part of acetone solvent after, then add 5 parts of HDPE (60550) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 27 parts of mLLDPE (ECD 350) and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 9
(1) preparation of the weather-proof master batch of mLLDPE: difference is not add mLLDPE-g-MAH grafts in the weather-proof master batch preparation process of mLLDPE, and other processes are identical with embodiment 6, make the weather-proof master batch of mLLDPE (b-2).
(2) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 9, difference is that the weather-proof master batch of the mLLDPE adding in composition preparation process is not containing mLLDPE-g-MAH grafts, 28 parts of the add-ons of the weather-proof master batch of mLLDPE (b-2), that is: 0.014 part of BPO and 0.17 part of TBHP are mixed with 0.5 part of acetone solvent after, then add 5 parts of HDPE (60550) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 28 parts of weather-proof master batches of mLLDPE (b-2) and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
Comparative example 10
(1) preparation of the weather-proof master batch of mLLDPE: difference is not add mLLDPE-g-MAH grafts in the weather-proof master batch preparation process of mLLDPE, and other processes are identical with embodiment 10, make the weather-proof master batch of mLLDPE (c-1).
(2) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 10, difference is that the weather-proof master batch of the mLLDPE adding in composition preparation process is not containing mLLDPE-g-MAH grafts, 29 parts of the add-ons of the weather-proof master batch of mLLDPE (c-1), that is: 0.015 part of BPO and 0.15 part of TBHP are mixed with 0.5 part of xylene solvent after, then add 5 parts of HDPE (60550) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 29 parts of weather-proof master batches of mLLDPE (c-1) and premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; After reaction 4min, extrude, cooling, granulation, prepare polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance is in Table 1 after tested.
The physical property measurement result of table 1 polyvinyl piping materials
Claims (7)
1. a polyethylene pipe resins composition, the weight of HDPE of take is absolutely, it is characterized in that comprising:
1)HDPE 100％；
2) composite crosslinking coagent 0.05%～0.2%;
3) the weather-proof master batch 10%～30% of mLLDPE;
The blend that the weather-proof master batch of described mLLDPE is comprised of mLLDPE, composite light stabilizer, mLLDPE-g-MAH grafts and dispersion agent; Described composite crosslinking coagent is that tertbutyl peroxide and dibenzoyl peroxide form, and the mass ratio of two kinds of linking agents is 25: 1～5: 1; The compound system that described composite light stabilizer is comprised of quencher and radical scavenger; The preparation method of the described weather-proof master batch of mLLDPE comprises: by the weight percent meter of mLLDPE, together with the mLLDPE of 100 parts and the mLLDPE-g-MAH grafts of 3～8 parts, the dispersion agent of 0.5～1.0 part, put in super mixer high-speed mixing 3～5min; And then add the composite light stabilizer of 0.11～0.54 part, high-speed mixing 5～10min; Mixed material is added to twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, obtains the weather-proof master batch of mLLDPE.
2. resin combination as claimed in claim 1, is characterized in that described mLLDPE-g-MAH grafts is maleic anhydride monomer to be grafted to the graft copolymer on mLLDPE main chain under the effect of initiator.
3. resin combination as claimed in claim 1, it is characterized in that described quencher is two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel, 2,2-thiobis (the tertiary octyl phenol oxygen of 4-base) nickel-n-Butyl Amine 99 complex compound, 2,2-thiobis (the tertiary octyl phenol oxygen of 4-base) nickel, dioctyl dithiocarbamic acid nickel, N, a kind of in N-nickel dibutyl dithiocarbamate, by the weight percent meter of mLLDPE, its consumption is 0.01%～0.04%.
4. resin combination as claimed in claim 1, is characterized in that described radical scavenger is hindered amine as light stabilizer, and by the weight percent meter of mLLDPE, its consumption is 0.1%～0.5%.
5. resin combination as claimed in claim 1, is characterized in that described dispersion agent is one or more in sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax.
6. resin combination as claimed in claim 1, the preparation method who it is characterized in that described mLLDPE-g-MAH grafts is: by the weight percent meter of mLLDPE, by the maleic anhydride of 5～10 parts and acetone, be within 1: 3～1: 5, to be mixed with mixing solutions by weight, by the mLLDPE high-speed mixing 3～5min of mixing solutions and 100 parts, the material mixing is placed to 1～2h in encloses container again; Then initiator and the acetone of getting 0.01～0.1 part are 1:10～1 by weight: 20 are mixed with mixing solutions, again by mixing solutions and the mixture high-speed mixing 3～5min placing, finally by carrying out melting graft reaction in twin screw extruder, 160～220 ℃ of temperature of reaction, reaction times 3～5min, extrude, cooling, granulation, obtain maleic anhydride grafting ratio and be 1%～3% mLLDPE-g-MAH grafts.
7. the preparation method of a resin combination as claimed in claim 1, it is characterized in that comprising: after first two kinds of crosslinking coagents are composite in proportion, add solvent, add again the HDPE that accounts for gross weight 5%～10%, then, after high-speed mixing 3～5min, make premix masterbatch; Then remaining HDPE, premix masterbatch and the weather-proof master batch of mLLDPE are joined together and in forcing machine, carried out extrusion reaction by charging opening, temperature of reaction is 160～220 ℃, reaction times is 3～5min, extrudes, cooling, granulation, makes polyethylene pipe resins composition.
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| CN105566573B (en) * | 2014-10-09 | 2018-05-04 | 中国石油化工股份有限公司 | High fluidity metallocene ldpe resin graft and preparation method thereof |
| WO2017116843A1 (en) * | 2015-12-29 | 2017-07-06 | Dow Global Technologies Llc | Highly grafted ethylene-based polymers, highly grafted ethylene-based polymer compositions, and processes for forming the same |
| CN106589517B (en) * | 2016-10-21 | 2019-07-23 | 四川大学 | A kind of bridge cable casing and preparation method thereof |
| CN108929477B (en) * | 2018-08-22 | 2020-09-22 | 温州市星峰新材料有限公司 | Color-change-resistant high-strength polyethylene pipe and preparation method thereof |
| CN109306109A (en) * | 2018-09-14 | 2019-02-05 | 曼瑞德集团有限公司 | A kind of thermoplasticity cross-linking polyethylene materials, preparation method and applications |
| CN109506054A (en) * | 2018-12-28 | 2019-03-22 | 瑞好环境科技(上海)有限公司 | A kind of aluminum plastic composite pipe and preparation method thereof |
| CN111825904B (en) * | 2019-04-17 | 2022-10-04 | 国家能源投资集团有限责任公司 | Polyethylene composition capable of being processed and formed, preparation method thereof and polyethylene product |
| CN111675842B (en) * | 2020-07-01 | 2023-03-28 | 上海中塑管业有限公司 | Be used for polyolefin gas tubular product and performance detection device thereof |
| CN114479225B (en) * | 2020-10-23 | 2023-10-20 | 中国石油化工股份有限公司 | Stress cracking-resistant polyethylene sheath material for bridge cable and preparation method thereof |
| CN112795076A (en) * | 2020-12-28 | 2021-05-14 | 金发科技股份有限公司 | Special material for low-temperature-resistant polyethylene anticorrosive coating and preparation method and application thereof |
| CN114752128A (en) * | 2022-04-28 | 2022-07-15 | 江苏恒峰线缆有限公司 | Preparation method of HDPE (high-density polyethylene) composite pipe material |
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